Dyestuffs of the phthalocyanine series



UNITED STATES PATENT DYESTUFFS OF THE PHTHALOCYANINE SERIES Hans Hoyer, Leverkusen-I. G. Werk, Rudolf Schriiter, Leverkusen-Schlebusch, and Heinrich Rinke, Leverkusen-Kuppersteg, Germany, assignors to General Aniline & Film Corporaticn, a corporation of Delaware No Drawing. Application June 13, 1938, Serial No. 213,458. In Germany June 1, 1937,

2 Claims. (01. 260-314) The present invention relates to new substanwith aromatic o-dicarboxylic acids, for instance tive dyestuffs of the phthalocyanine series. diphenyl-o-dicarboxylic acids. In this case there The compounds which are prepared in accordare obtained phthalocyanines containing less ance with our present invention may be defined than 4, for instance two carboxylic acid groups. as phthalocyanines of the benzene series at least The solubility of the resulting dyestuffs can be one of the benzene nuclei of which is substituted varied by subjecting them either to a decarby one carboxylic acid group and one phenyl boxylating or sulfonating process.

group. These compounds are characterized by As suitable starting material for the new dyetheir being capable of directly dyeing cellulosic stuffs there may be mentioned the l-phenylbenmaterials such as cotton, viscose or ouprammozene-2.4.5-tricarboxylic acid which can be obnium silk, paper and the like. They show very tained by the action of 2.3-d-imethylbutadiene clear green shades and are distinguished by exon cinnamic acid followed by dehydrogenation cellent fastness properties. They are furtherand oxidation according to the following scheme:

CH3 CH3 CH3 CH3 E E i on 00 H2o /CH1 1 a 7 c0011 coon 7 more capable of being converted into valuable The following examples illustrate the present lake dyestuffs by neutralizing the same, for ininvention without, however, restricting it thereto stance by means of alkaline earth metals, the the parts being by weight: Y e pigments thus obtained showing also extremely good fastness properties. Particular importance Example 1 is attached to the copper containing dyestufis To a mixture of 100 parts of 1-phenyl-2.4.5-

as they show the clearest shade. benzene tricarboxylic acid and 300 parts of urea Our new dyestufis can be prepared by startthere are added at 150 C. 25 parts of copper ing from such diphenyls as contain in one of the chloride, 1 p t O ammonium molybdate d benzene nuclei three carboxylic acid groups, at 1 part of boric acid. The reaction mixture is least two of which are in o-position to each then heated to 200 C. and kept at this temother, and heating the same in a manner known 40 perature until the formation of the dyestufi is per se with a metal salt and urea, preferably complete. After cooling the melt is dissolved in the presence of catalysts such as boric acid in hot dilute caustic soda lye and freed from and/or salts of an acid H2XO4 wherein X stands the precipitated copper oxide by filtration, for an element of the fifth group of the periodic whereupon the tetraphenyl copper phthalocyasystem. The starting materials as Well as the nine tetracarboxylic acid is precipitated by acidfinal products may contain various substituents ification, filtered, washed until neutral and dried. without departing from the scope of the present The dyestuff thus obtained represents a green invention. Thus, they may contain chlorine powder with a metallic lustre which is easily atoms, alkyl-, or alkoxy groups in those benzene soluble in aqueous alkalies and dyes cellulose nuclei, which are free from the carboxylic acid containing materials such as cotton, viscose or groups. The said starting materials can also be copper silk in vivid yellowish-green shades. The applied in admixture with other starting matetraphenyl-copper phthalocyanine tetracarboxterials known to be capable of forming phthaloylic acid yields insoluble metal salts when cyanines, the dyestuffs thus formed containing treated with calcium or barium salts and the different substituents in the molecule. Thus, like, and may be used in this form on a suitable there can be employed mixtures of diphenylsubstrate such as aluminium oxide hydrate and tricarboxylic acids of the character described the like as pigments.

Example 2 parts of 4-chlorodiphenyl-2.4.5-tricarboxylic acid and 15 parts of urea are heated for /2 hour to 150. Thereupon 1 part of anhydrous copper chloride, 01 part of ammonium molybdate are added and the reaction mixture-is heated to 180-190", until the formation of the dyestufi is complete. The melt is then boiled out with dilute hydrochloric acid, the remaining dyestufi" which represents a green powder being sucked oil and dried. The alkali metal salt of the tetrachlorophenyl copper phthalocyanine tetracarboxylic acid thus obtained dyes cotton or any other cellulose containing material in brilliant green shades.

Example 3 5 parts of 4'-methoxydiphenyl-2.4.5-tricarboxylic acid and 15 parts of urea are heated for hour to 150-160; thereupon 1 part of anhydrous copper chloride and 0.1 partofammonium molybdate are added and the whole is heated to.180-190.. After several hours themelt is extracted with boiling dilute hydrochloric acid and the tetra methoxyphenyl copper phthalocyanine tetracarboxylic acid is suckedofi. The dyestuff dyes cellulose containing materials such as cotton from an alkaline solution brilliant yellowish-green shades.

Example 4 5 parts of .2 chlorodiphenyl 2.4.5 tricarboxylic'acid and 15 parts of urea are heated for /2 hour to 150-160"; thereupon a mixture of 1 part of anhydrous copper chloride, and 0.1 part of ammonium molybdate is added and the whole is heated to 180190 until the formation of the dyestuff is complete. The melt is then digested with hot hydrochloric acid and the tetrachlorophenyl copper phthalocyanine tetracarboxylic acid is sucked off. The dyestuff thus obtained dyes cotton in bluish-green shades.

Example 5 An intimate mixture of Parts Diphenyl-Z.4.5-tricarboxylic acid Urea 30 Nickel chloride 2 Ammonium molybdate 0.4

is heated to 180-l90 until the reaction mixture is completely converted into the phthalocyanine 'dyestufi. Then the crude product is digested with hot dilute hydrochloric acid to remove the excess of nickel chloride, sucked ofi, washed until neutral and dried. The dyestuif thus obtained is easily soluble in aqueous alkali and yields on cotton and the like bright green shades of extremely good fastness.

In the naming of the products of our process it should be noted that the numbering of the positions substituted by the phenyl and carboxy groups does not correspond with the same numbered positions in that diphenyl-2.4.5-tricarboxylic acid starting material. The 4 and 5 carbon atoms of the starting material carrying the ortho-carboxylic acid groups form a part of the pyrrole ring of the isoindole nuclei of the phthalocyanine molecule, whereas the 4 and 5 positions of thephthalocyanine molecule are the outside carbon atoms, which maybe referred to as the para positions andwhich carry substitutable hydrogen. This I system of naming substituted phthalocyanines has been used by Miles A. Dahlen inhis article, The phthalocyanines, Industrial and Engineering Chemistry, vol. 31 (1939), pages 8394347. It is'used in the appended claims to designate the positions of attachment of the car- .boxylic acid and phenyl group.

HANS HoYnR. RUDOLF scHR6TER. HEINRICH RINKE. 

